Increasing BioIncreasing Bio--Availability of Availability of Contaminants In Groundwater Using Contaminants In Groundwater Using Surfactant Enhanced Bioremediation Surfactant Enhanced Bioremediation

(SEB)(SEB)

Water Technologies Symposium 2009 Water Technologies Symposium 2009 April 29, 30 & May 1, 2009April 29, 30 & May 1, 2009Fairmont Banff SpringsFairmont Banff Springs

Banff, AlbertaBanff, Alberta

Presentation OutlinePresentation Outlinei)i)Definition of bioDefinition of bio--availability;availability;ii)ii)Facts affecting bioFacts affecting bio--availability;availability;iii)iii)BioBio--availability of F1, F2, F3 and F4; availability of F1, F2, F3 and F4; iv)iv)Contaminant sorption explained;Contaminant sorption explained;v)v)How sorption affects bioHow sorption affects bio--availability;availability;vi)vi)Surfactants explained;Surfactants explained;vii)vii)How Surfactants can improve desorption How Surfactants can improve desorption & increase bio& increase bio--availability;availability;viii)viii)Case studies;Case studies;ix)ix)Questions & Answers PeriodQuestions & Answers Period

BioBio--availability & Sorptionavailability & Sorption‘…‘…During the past decade, much discussion has During the past decade, much discussion has

centered on the unavailability of absorbed and centered on the unavailability of absorbed and adsorbed compounds to soil microorganisms. It is adsorbed compounds to soil microorganisms. It is

generally now assumed that desorption and generally now assumed that desorption and diffusion of bound contaminants to the aqueous diffusion of bound contaminants to the aqueous phase is required for microbial degradationphase is required for microbial degradation…’…’

Ref: W.P. Inskeep, J.M. Wraith, C.G. Johnston, Hazardous SubstanRef: W.P. Inskeep, J.M. Wraith, C.G. Johnston, Hazardous Substance ce Research Center, 2005.Research Center, 2005.

Definition Of BioDefinition Of Bio--AvailabilityAvailability

The degree to which, or rate at The degree to which, or rate at which, a contaminant that may be which, a contaminant that may be

dissolved or sorbed, becomes dissolved or sorbed, becomes available at the site of biological available at the site of biological

activity for uptake and activity for uptake and mineralization.mineralization.

FACTFACT90 to 95 % of all petroleum 90 to 95 % of all petroleum

hydrocarbon contaminants will hydrocarbon contaminants will absorb or adsorb to particles In absorb or adsorb to particles In

soil, sediments, bedrock and soil, sediments, bedrock and groundwater aquifersgroundwater aquifers

F2 to F3 to F4 F2 to F3 to F4

FACTFACTSorption is one of the most Sorption is one of the most

significant factors behind why significant factors behind why remediation can be costly, slow, remediation can be costly, slow,

and sometimes failand sometimes fail

Hydrocarbon Sorption PotentialsHydrocarbon Sorption PotentialsF4 >F3 >F2 >F1F4 >F3 >F2 >F1

FACTFACTContaminant Sorption Limits the Contaminant Sorption Limits the

‘‘AvailabilityAvailability’’ of Many Contaminants of Many Contaminants For Biological Remediation!For Biological Remediation!

Contaminants Must BeContaminants Must Be‘‘BioBio--AvailableAvailable’’ For Biodegradation For Biodegradation

To Be RealizedTo Be Realized

FACTFACTLow Low ‘‘BioBio--AvailabilityAvailability’’ Will Limit Will Limit

Contaminant Bioremediation Rate Contaminant Bioremediation Rate In Groundwater & SoilIn Groundwater & Soil

Hydrocarbon BioHydrocarbon Bio--AvailabilityAvailability

F1 >F2 >F3 >F4F1 >F2 >F3 >F4

Sorption (i.e. absorption or adsorption) of Sorption (i.e. absorption or adsorption) of Contamination in Soil MatrixContamination in Soil Matrix

Soil & Groundwater Bioremediation Must Soil & Groundwater Bioremediation Must Address This To Be Successful.Address This To Be Successful.

Adsorption vs. AbsorptionAdsorption vs. Absorption►►Sorption reactions generally occur over a short period of time, Sorption reactions generally occur over a short period of time, however if the however if the adsorbedadsorbed contaminant begins to be incorporated into contaminant begins to be incorporated into the structure of the sorbent , a slow occurring reaction, known the structure of the sorbent , a slow occurring reaction, known as as absorptionabsorption, begins to take place. , begins to take place.

►►To be more precise , the To be more precise , the difference between adsorption and difference between adsorption and absorptionabsorption is that adsorption is the attraction between the outer is that adsorption is the attraction between the outer surface of a solid particle and a contaminant, whereas absorptiosurface of a solid particle and a contaminant, whereas absorption is the n is the uptake of the contaminant into the physical structure of the soluptake of the contaminant into the physical structure of the solid. id.

►►The The next figure shows the differences next figure shows the differences between intrabetween intra--particle particle absorption versus surface adsorption. absorption versus surface adsorption.

►►The The main difference main difference being that some contaminant particles are being that some contaminant particles are attracted to the outer surface of the soil particle, while otherattracted to the outer surface of the soil particle, while others are s are incorporated into the particle's structure. incorporated into the particle's structure.

Adsorption vs. Absorption

Fine Grain Soil From Central AlbertaFine Grain Soil From Central AlbertaLots of surface area for contaminant sorptionLots of surface area for contaminant sorption

Sorption DemonstrationSorption Demonstration(Animation)(Animation)

The following animation sequence displays how sorption The following animation sequence displays how sorption can affect two separate particles' velocities and can affect two separate particles' velocities and

movement in an aquifer. movement in an aquifer.

The more they exhibit sorption, the less The more they exhibit sorption, the less ‘‘availableavailable’’ they they are for bioremediation. are for bioremediation.

The animation shows a vertical cut from a soil column, The animation shows a vertical cut from a soil column, interspersed particles of organic matter, and two interspersed particles of organic matter, and two

contaminants that are moving through the soil /water contaminants that are moving through the soil /water matrix. matrix.

‘‘Availability of ContaminationAvailability of Contamination’’Contaminant Contaminant ‘‘availabilityavailability’’ is quickly becoming is quickly becoming

a new driving force for the evaluation of a new driving force for the evaluation of inin--situ situ andand exex--situsitu remediation options for air, remediation options for air,

soil and groundwater remediation.soil and groundwater remediation.

Examples:Examples:‘‘BioBio--AvailabilityAvailability’’ BioremediationBioremediation

‘‘Chemical AvailabilityChemical Availability’’ Oxidation/ReductionOxidation/Reduction

‘‘PhysicalPhysical--AvailabilityAvailability’’ P&T, Soil Washing, etc.P&T, Soil Washing, etc.

Generally SpeakingGenerally Speaking

Contaminant Sorption Is Inversely Proportional Contaminant Sorption Is Inversely Proportional To Contaminant BioTo Contaminant Bio--Availability For Soil and Availability For Soil and

Groundwater BioremediationGroundwater Bioremediation

Hence:Hence:Hydrocarbon Sorption PotentialsHydrocarbon Sorption Potentials

F4 >F3 >F2 >F1F4 >F3 >F2 >F1

Hydrocarbon BioHydrocarbon Bio--AvailabilityAvailabilityF1 >F2 >F3 >F4F1 >F2 >F3 >F4

Hydrocarbon Degradation RatesHydrocarbon Degradation RatesF1 >F2 >F3 >F4F1 >F2 >F3 >F4

BIOREMEDIATIONBIOREMEDIATION►Bioremediation can be Bioremediation can be defineddefined as any process that uses as any process that uses

microorganisms or their enzymes to remove and or microorganisms or their enzymes to remove and or neutralize contaminants within the environment neutralize contaminants within the environment (i.e., within soil and water) to their original condition.(i.e., within soil and water) to their original condition.

►►Bioremediation can be employed to remediate specific Bioremediation can be employed to remediate specific types of contaminants such as: petroleum hydrocarbons types of contaminants such as: petroleum hydrocarbons (F1, F2, F3, F4), PAH, PCB, chlorinated solvents, (F1, F2, F3, F4), PAH, PCB, chlorinated solvents, pesticides pesticides -- all of which can be biodegraded by all of which can be biodegraded by microorganisms given proper treatment conditions. microorganisms given proper treatment conditions.

Aerobic Aerobic In the presence of sufficient oxygen (aerobic conditions), In the presence of sufficient oxygen (aerobic conditions), and other nutrient elements, microorganisms will and other nutrient elements, microorganisms will ultimately convert many organic contaminants to carbon ultimately convert many organic contaminants to carbon dioxide, water, and microbial cell mass. dioxide, water, and microbial cell mass. Hydrocarbon Hydrocarbon Bioremediation is an aerobic biodegradation process.Bioremediation is an aerobic biodegradation process.

AnaerobicAnaerobicIn the absence of oxygen (anaerobic conditions), the In the absence of oxygen (anaerobic conditions), the organic contaminants will be ultimately metabolized organic contaminants will be ultimately metabolized limited amounts of carbon dioxide, and trace amounts of limited amounts of carbon dioxide, and trace amounts of hydrogen gas. hydrogen gas. Reductive Reductive dechlorinationdechlorination is anaerobicis anaerobic..

BIOSTIMULATIONBIOSTIMULATIONWhere you stimulate existing microorganisms in the soil Where you stimulate existing microorganisms in the soil

though addition of amendments to degrade the though addition of amendments to degrade the contaminants present. This assumes the bacteria capable contaminants present. This assumes the bacteria capable

of breaking down the contaminants are present in soil. of breaking down the contaminants are present in soil.

BIOAUGMENTATIONBIOAUGMENTATIONWhere you add microorganism as part of the amendment Where you add microorganism as part of the amendment

process to achieve bioremediation of the subject soilsprocess to achieve bioremediation of the subject soils

ENHANCED BIODEGRADATIONENHANCED BIODEGRADATIONThe use of special chemical additives, such as Surfactants The use of special chemical additives, such as Surfactants

(SEB(SEB--Surfactant Enhanced Bioremediation) to help with Surfactant Enhanced Bioremediation) to help with the desorption of contaminants and nutrients making the desorption of contaminants and nutrients making

them more Biothem more Bio--Available to the bacteria during Available to the bacteria during BioBio--stimulation or Biostimulation or Bio--augmentation.augmentation.

‘‘Newest Innovative Form of BioremediationNewest Innovative Form of Bioremediation’’

For Effective Bioremediation of For Effective Bioremediation of Petroleum Contaminated Petroleum Contaminated

Groundwater & SoilGroundwater & Soil

YOU MUST ADDRESS SORPTIONYOU MUST ADDRESS SORPTION

Sorption = Limited BioSorption = Limited Bio--AvailabilityAvailability

Contaminant sorption is a major limiting Contaminant sorption is a major limiting factor negatively affecting all factor negatively affecting all inin--situsitu & & exex--situsitu remediation of F2, F3, and F4 remediation of F2, F3, and F4 contaminantscontaminants

SURFACTANT ENHANCED SURFACTANT ENHANCED BIOREMEDIATION BIOREMEDIATION

(SEB)(SEB)

New Innovative Process to New Innovative Process to DesorbDesorb F2, F3, F2, F3, and F4 Contaminants Making Them and F4 Contaminants Making Them

BioBio--Available For Bioremediation In Available For Bioremediation In Groundwater & SoilsGroundwater & Soils

Overview of Surfactants & SEB Overview of Surfactants & SEB Case StudiesCase Studies

Surface Active Agent (SAA) with Hydrophilic Surface Active Agent (SAA) with Hydrophilic (water loving) and (water loving) and Lipophilic(oilLipophilic(oil--liking) endsliking) ends

Structure & DefinitionStructure & Definition

• Surface Active Agent• Anionic - negatively charged

groupings (laundry detergent)• Cationic - positively charged

groupings (germicides, emulsifiers)• Amphoteric have both anionic and

cationic groupings (i.e. Hair shampoo, skin cleaner, and carpet shampoo)

• Non-Ionic - no ionic constituents. Selectively dissolve LNAPL, DNAPL, PAHs, DCE, TCE, PCE, etc.

Surfactants Can Lower Water Surface TensionSurfactants Can Lower Water Surface Tension(From 73 dynes to <50 dynes) & (From 73 dynes to <50 dynes) & DesorbDesorb SorbedSorbed

Contaminants From Soil SurfacesContaminants From Soil Surfaces

This can increase the wetting ability of the water when This can increase the wetting ability of the water when present, making surfactant application possible in fine present, making surfactant application possible in fine

grain soils by improving water Permeability (K).grain soils by improving water Permeability (K).

They can improve desorption in finer grain soils aiding They can improve desorption in finer grain soils aiding bioremediation by increasing biobioremediation by increasing bio--availabilityavailability

Functional Groups

Surfactant Interaction With Organic (NAPL) On A Surfactant Interaction With Organic (NAPL) On A Surface With Partial Micelle of F2, F3, or F4Surface With Partial Micelle of F2, F3, or F4

MechanismMechanism

InIn--situ & Exsitu & Ex--situ SEB situ SEB

ApplicationsApplications&&

Case Studies Case Studies

In-Situ SEBSurfactant Enhanced Bioremediation

InIn--Situ SEB Situ SEB Zone Zone ---------->>

Ex-Situ SEBSurfactant Enhanced Bioremediation (F3 &F4)

SEB ApplicationsSEB ApplicationsCase Studies Case Studies

CASE STUDY #1Research Project (SEB)

Madrid Spain

In 2007In 2007--2008, Ivey international Inc. conducted a joint Research and 2008, Ivey international Inc. conducted a joint Research and Development project with CIEMAT in Madrid Spain.Development project with CIEMAT in Madrid Spain.

Purpose was to evaluate the ability of Surfactant (IveyPurpose was to evaluate the ability of Surfactant (Ivey--sol 106) to sol 106) to DesorbDesorb SorbedSorbed PAH compounds in column tests. PAH compounds in column tests.

If effective; to evaluate potential for increasing the BioIf effective; to evaluate potential for increasing the Bio--Availability of Availability of PAH for biodegradation using the SEB process.PAH for biodegradation using the SEB process.

Images of column test laboratory set upImages of column test laboratory set up

PAHs desorption in free desorption test water only.

Free desorption

0.010.020.030.040.050.060.070.080.0

HAP

PA

Hs

Des

optio

n (%

)

Fluorene Phenanthrene Anthracene

Fluoranthene Pyrene Benzo(a)anthracene

Chrysene Benzo(b)f luoranthene Benzo(k)fluoranthene

Benzo(a)pyrene Dibenzo(a,h)anthracene Benzo(g,h,i)perylene

PAH = HAP PAH = HAP (Spanish)(Spanish)

PAHs desorption in induced desorption test (with a resin)

Induced desorption with resin (XAD-2)

0.010.020.030.040.050.060.070.080.0

HAP

PA

Hs D

esor

ptio

n (%

)

Fluorene Phenanthrene Anthracene

Fluoranthene Pyrene Benzo(a)anthracene

Chrysene Benzo(b)f luoranthene Benzo(k)fluoranthene

Benzo(a)pyrene Dibenzo(a,h)anthracene Benzo(g,h,i)perylene

PAHs desorption with Ivey-sol 106 aided desorption test

Surfactant desorption (Ivey sol 106)

0.0

10.0

20.0

30.040.0

50.0

60.0

70.0

80.0

HAP

PAHs

Des

orpt

ion

(%)

Fluorene Phenanthrene AnthraceneFluoranthene Pyrene Benzo(a)anthraceneChrysene Benzo(b)f luoranthene Benzo(k)f luorantheneBenzo(a)pyrene Dibenzo(a,h)anthracene Benzo(g,h,i)perylene

Comparative PAHs desorption (%) for all testsFl

uore

ne

Phen

anth

rene

Anth

race

neFlu

oran

thene

Pyre

ne

Benz

o(a)

anthr

acen

eChr

ysen

e

Benz

o(b)

fluor

anth

ene

Benz

o(k)

fluor

anth

ene

Benz

o(a)

pyre

ne

Dibenz

o(a,

h)an

thra

cene

Benz

o(g,

h,i)p

eryle

ne

FreeResin

Ivey-sol 106

0.005.00

10.0015.0020.0025.0030.0035.0040.0045.0050.00

PAHs desorption (%)

HAP

Product

Free Resin Ivey-sol 106

Conclusions

• Ivey-sol 106 surfactants were very effective at desorbing the PAH compounds making them more ‘Available’ for all forms of remediation

• The potential for Ivey-sol surfactant to desorb and increase the bio-availability of PAH compounds for bioremediation was established.

• The findings of this study are to be published in an international journal in 2009

• Continued joint research and development projects, stemming fromthis work, are planned in 2009.

Case Study #2: SEB Groundwater Treatment (Bioreactor)

Near Chicago, USA

Multi-Stage Bioreactor TPH Water Treatment

Packing Material (Growth Substrate)

Typical Bacterial Growth on substrate

to treat the water(No Ivey-sol)

A bio-reactor post (24 Hour) following Ivey-sol Addition

Conclusions

• The addition of Ivey-sol as an in-line automated feed to the bio-reactor water treatment system, significantly increased the rate and extent of biological growth on the packing substrate.

• According to the subject client, who also tested competing products, he stated that Ivey-sol out performed all other surfactants.

• The Ivey-sol made the dissolved contaminants more bio-available to the bacteria within the bio-reactors as was evidenced by visual bacterial growth in <24 to <48 hours.

CASE STUDY #3Surfactant Enhanced Bioremediation (SEB) of F2, F3

and F4 Contaminated Soils Northern Alberta

►Ivey International Inc. was retained to apply their SEB technology to treat >2000 tons of F2, F3, and F4 fine-grained contaminated soil at a remote site in Northern Alberta, Canada.

►The project commenced in late August 2006, just prior to the onset of colder northern weather in an area known for -30 oC to -40oC winter temperatures.

Ex-Situ SEBSurfactant Enhanced Bioremediation (F3 &F4)

Ex-situ Surfactant Enhanced Bioremediation(SEB) of F2, F3, F4 Soil

Contamintion

0

500

1000

1500

2000

2500

Aug 2006 Feb 2007 July 2007

ppm

(mg/

kg)

F1

F2

F3

F4

RESULTS

F1 F2 F3 F4

August 2006 441 ppm 1,189 ppm 2,064 ppm 965 ppm

February 2007 2 ppm 376 ppm 1,107.5 ppm 347.5 ppm

July 2007 N.D. 98.25 ppm 347.5 ppm 180 ppm

CONCLUSIONS►The SEB process was effective in achieving the soil remediation goals in <11 months, commencing with average baseline hydrocarbon concentration of F1 441 ppm, F2 1,189 ppm, F3 2,064 and F4 965.

► The total % reduction in each hydrocarbon fractions were: F1 (100%), F2 (92%), F3 (83%), and F4 (81%), meeting the applicable Alberta Environment Soil Remediation Guidelines (ABENV, June 2007).

For Additional InformationContact:

George A. Ivey, B.Sc., CEC, CES, CESAPresident & Senior Remediation Specialist

Ivey International Inc.Tel: + 250 923 6326Fax: + 250 923 0718

Email: budivey@island.netWeb: www.ivey-sol.com

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